US11999688B2 - Method for producing dicarboxylic acid - Google Patents

Method for producing dicarboxylic acid Download PDF

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US11999688B2
US11999688B2 US17/253,779 US201817253779A US11999688B2 US 11999688 B2 US11999688 B2 US 11999688B2 US 201817253779 A US201817253779 A US 201817253779A US 11999688 B2 US11999688 B2 US 11999688B2
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cyclohexene
catalyst
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Shengjun Huang
Dazhi Zhang
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Dalian Institute of Chemical Physics of CAS
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    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
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Definitions

  • the present application relates to a method for producing dicarboxylic acid, which belongs to the new technical field of chemical production and manufacturing.
  • Dicarboxylic acid is an important chemical precursor material in polymer chemical industry and organic synthesis.
  • Adipic acid is a representative substance among dicarboxylic acids. At present, it is mainly produced through the oxidation of cyclohexanol/cyclohexanone. Representative production routes are as follows: 1) cyclohexane is oxidized to produce cyclohexanol-cyclohexanone (KA oil) which is then oxidized to produce adipic acid; 2) cyclohexene is hydrated to produce cyclohexanol which is then oxidized to produce adipic acid.
  • the single-pass conversion rate of cyclohexane is low in the step of cyclohexane oxidation to KA oil, which is less than 6%, and the operating conditions of the reaction process are not easy to control which would easily incur accidents.
  • the hydration of cyclohexene has significant advantages in operating safety of the reaction process.
  • U.S. Pat. No. 5,166,421 disclosed a method for producing adipic acid by twice hydroformylation with butadiene as raw materials. The total yield of adipic acid by this route is not high, but the cost of the precious metal catalyst used is relatively high.
  • GB1402480 disclosed a method of firstly carrying out an addition reaction between cyclic mono-olefin and saturated aliphatic dibasic acid containing from 4 to 12 carbon atoms to generate corresponding dibasic esters, and then oxidizing the resulted esters to produce dicarboxylic acids.
  • reaction raw materials used in the addition reaction are solid-liquid two-phase, such method can only be operated intermittently, and thus the reaction efficiency is not high, and the final product and the raw materials are not easy to separate. Therefore, based on the current state of the art, it is still necessary to develop a new method for producing dicarboxylic acid, which should possess the characteristics of safe operating conditions, fast reaction rate, high reaction conversion rate and high atom utilization.
  • a method for producing dicarboxylic acid comprises the following steps:
  • the cyclic olefin is selected from the compound with the chemical formula represented by formula I, the compound with a chemical formula represented by formula II, the compound with the chemical formula represented by formula III, the compound with the chemical formula represented by formula IV, and any combination thereof:
  • the lower monocarboxylic acid is selected from at least one compound with a chemical formula represented by formula V:
  • the lower monocarboxylic acid especially acetic acid
  • the cyclic olefin has better mutual solubility with the cyclic olefin.
  • the contact between the reactants is thus better, and the ratio of reactants can be adjusted in a wider range, which can have higher reactivity and selectivity.
  • the reaction mixture of acetic acid and cyclic olefin is liquid phase, and thus the reaction in the present invention can be continuously operated using a fixed bed, which has higher efficiency.
  • the intermediate product (such as cyclohexyl acetate) of the addition reaction obtained by using the saturated monocarboxylic acid of the present invention as raw material is liquid.
  • the use of liquid cyclohexyl acetate is more advantageous to the subsequent oxidation operation, the oxidation reaction step can be operated continuously, and the reaction speed is faster and the selectivity is higher.
  • the dicarboxylic acid product obtained after the oxidation reaction of the present invention is easier to be separated from the saturated monocarboxylic acid.
  • the saturated monocarboxylic acid used in the present invention is cheaper.
  • the addition reaction catalyst in step 1) comprises at least one of a supported inorganic acid, a cation exchange resin and a molecular sieve.
  • the acid catalyst is solid acid catalyst.
  • the supported inorganic acid catalyst contains an inorganic acid and a support; the inorganic acid is selected from sodium hydrogen sulfate, sodium hydrogen phosphate, AlCl 3 , heteropoly acid and any combination thereof, and the support is selected from silica, diatomite, kaolin and any combination thereof, wherein the weight percentage of the inorganic acid in the supported inorganic acid ranges from 5% to 25%.
  • the cation exchange resin is a sulfonic acid type-macroporous strong acid ion exchange resin whose Hammett index of acid strength is H 0 ⁇ 10, and the H + exchange capacity of the ion exchange resin is greater than 1.0 mmol/L;
  • the molecular sieve is selected from HY, H ⁇ and HZSM-5 molecular sieves with topological structures of FAU, BEA, and MFI, and any combination thereof; and as measured by NH 3 chemisorption determination, the molecular sieve has a weak acid site density ranging from 0.005 mmol/g to 0.35 mmol/g, a medium-strength acid site density ranging from 0.01 mmol/g to 0.5 mmol/g, and a strong acid site density ranging from 0.003 mmol/g to 0.15 mmol/g.
  • the molar ratio of the lower monocarboxylic acid to the cyclic olefin is in a range from 0.2 to 10.0, and the space velocity of the cyclic olefin is in a range from 0.6 to 3.0 g g ⁇ 1 ⁇ h ⁇ 1 .
  • the molar ratio of the lower monocarboxylic acid to the cyclic olefin can be any value of 0.2, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or any value in the range determined by any two of 0.2, 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10.
  • the space velocity of the cyclic olefin can be 0.6 g ⁇ g ⁇ 1 ⁇ h ⁇ 1 , 1 g ⁇ g ⁇ 1 ⁇ h ⁇ 1 , 1.5 g ⁇ g ⁇ 1 ⁇ h ⁇ 1 , 2.0 g ⁇ g ⁇ 1 ⁇ h ⁇ 1 , 2.5 g ⁇ g ⁇ 1 ⁇ h ⁇ 1 , 3.0 g ⁇ g ⁇ 1 ⁇ h ⁇ 1 or any value in the range determined by any two of 0.6 g ⁇ g ⁇ 1 ⁇ h ⁇ 1 , 1 g ⁇ g ⁇ 1 ⁇ h ⁇ 1 , 1.5 g ⁇ g ⁇ 1 ⁇ h ⁇ 1 , 2.0 g ⁇ g ⁇ 1 ⁇ h ⁇ 1 , 2.5 g ⁇ g ⁇ 1 ⁇ h ⁇ 1 , 3.0 g ⁇ g ⁇ 1 ⁇ h ⁇ 1 .
  • the addition reaction is carried out in one or more reactors, and the reactor is selected from a fixed bed reactor, a kettle-type reactor and combination thereof.
  • the addition reaction is carried out under a pressure ranging from 0.1 to 2.0 MPa, and a reaction temperature ranging from 50 to 150° C.
  • the pressure for carrying out the addition reaction may be any value of 0.1 MPa, 0.5 MPa, 1.0 MPa, 1.5 MPa, 2.0 MPa or any value in the range determined by any two of 0.1 MPa, 0.5 MPa, 1.0 MPa, 1.5 MPa, and 2.0 MPa.
  • the lower limit of the temperature for carrying out the addition reaction is selected from a range from 50 to 60° C., any value within the range from 50 to 60° C. or any sub-range within the range from 50 to 60° C.
  • the upper limit of the temperature for carrying out the addition reaction is selected from a range from 130 to 150° C., any value within the range from 130 to 150° C. or any sub-range within the range from 130 to 150° C.
  • the oxidation reaction in step 2) is carried out at a reaction temperature ranging from 40 to 120° C., and a reaction pressure ranging from 0.1 to 0.5 MPa.
  • the lower limit of the temperature for carrying out the oxidation reaction is selected from a range from 40 to 50° C., any value within a range from 40 to 50° C., or a sub-range within the range from 40 to 50° C.
  • the upper limit of the temperature for carrying out the oxidation reaction is selected from a range from 100 to 120° C., any value within the range from 100 to 120° C., or any sub-range within the range from 100 to 120° C.
  • the oxidant in step 2) is selected from HNO 3 , nitrite, hydrogen peroxide solution, and any combination thereof.
  • the oxidation catalyst in step 2) is selected from NH 4 VO 3 , Cu(NO 3 ) 2 , Co(NO 3 ) 2 , Fe(NO 3 ) 3 , ammonium molybdate, ammonium tungstate, heteropoly acid and any combination thereof.
  • the amount of the oxidation catalyst satisfies that: after the oxidation catalyst is added, the mass concentration of each oxidation catalyst in the oxidation reaction system ranges from 0.01% to 1.0%.
  • each oxidant there can be one or more oxidants.
  • the mass concentration of each oxidant is calculated separately.
  • the intermediate product system comprising the cyclic carboxylic acid ester is a mixed system after the addition reaction is completed or only refers to the cyclic carboxylic acid ester.
  • the method for producing dicarboxylic acid further comprises the step 3):
  • the cyclic olefin and carboxylic acid as raw materials are separately fed into a fixed bed reactor loaded with a certain amount of solid catalyst.
  • the reaction pressure ranges from 0.1 to 2.0 MPa
  • the reaction temperature ranges from 50 to 150° C.
  • the space velocity of cyclic olefin ranges from 0.6 to 3.0 g ⁇ g ⁇ 1 ⁇ h ⁇ 1
  • the molar ratio of the lower monocarboxylic acid to the cyclic olefin ranges from 0.2 to 10.0.
  • the reaction pressure ranges from 0.1 to 1.1 MPa
  • the reaction temperature ranges from 70 to 125° C.
  • the space velocity of the cyclic olefin ranges from 0.6 to 2.0 g ⁇ g ⁇ 1 ⁇ h ⁇ 1
  • the molar ratio of the lower monocarboxylic acid to the cyclic olefin ranges from 1 to 6.
  • the obtained product is separated by distillation to obtain a cyclic carboxylic acid ester product with purity thereof greater than 99.5% or a mixture of a cyclic carboxylic acid ester and a corresponding carboxylic acid.
  • the steps of the oxidation reaction are as follows: a certain amount of oxidant is added to the kettle-type reactor and a certain amount of catalyst is added therein, which are then stirred and dissolved at a certain speed (in a range from 100 to 300 rmp/min).
  • the mass concentration of each catalyst in the solution ranges from 0.01% to 1.0%.
  • the temperature of the reactor is raised to the reaction temperature, and then the cyclic carboxylic acid ester or a mixture of the cyclic carboxylic acid ester and the corresponding carboxylic acid is added therein.
  • the reaction temperature ranges from 40 to 120° C., and the molar ratio of nitric acid to cyclic carboxylic acid ester ranges from 3 to 15.
  • the reaction is stopped.
  • the resulted product is cooled, crystallized and separated, washed and purified to obtain the corresponding dicarboxylic acid.
  • FIG. 1 shows the changes in the conversion rate of cyclohexene and the selectivity of cyclohexyl acetate over time in Example 32.
  • Analysis of the product obtained from the addition reaction comprises: the composition of the collected product from the addition reaction is quantitatively analyzed by the Agilent 7890B gas chromatograph equipped with FID detector.
  • the gas chromatographic column is selected from FFAP chromatographic column.
  • n-butanol is used as the internal standard for quantitative analysis of the product.
  • the composition of the collected product from the oxidation reaction is quantitatively analyzed by the Maple S6000 liquid chromatography.
  • the liquid chromatographic column is selected from HSS-T3 chromatographic column for analysis.
  • the product obtained from the addition reaction was distilled to obtain cyclohexyl acetate with a purity greater than 99.5%.
  • the cyclohexyl acetate was further subjected to an oxidation reaction, and the specific steps of the oxidation reaction were as follows: 145.5 g of 65% nitric acid is added to a 250 ml reactor, and 5.5 g of copper nitrate trihydrate and 0.17 g of ammonium metavanadate as catalysts were added therein respectively.
  • the temperature of the reactor was raised to 70° C. Vigorous stirring was performed to dissolve the catalyst. 17.8 g of cyclohexyl acetate obtained from the addition reaction was added to the reaction solution. The reaction was performed under stirring conditions for 40 minutes.
  • the product obtained from the addition reaction was distilled to obtain cyclohexyl acetate with a purity greater than 99.5%.
  • the cyclohexyl acetate was further subjected to an oxidation reaction, and the specific steps of the oxidation reaction were as follows: 121.2 g of 65% nitric acid was added to a 250 ml reactor, and 3.7 g of copper nitrate trihydrate and 0.11 g of ammonium metavanadate as catalysts were added therein respectively. The temperature of the reactor was raised to 70° C. Vigorous stirring was performed to dissolve the catalyst. 17.8 g of cyclohexyl acetate obtained from the addition reaction was added to the reaction solution. The reaction was performed under stirring conditions for 40 minutes.
  • the temperature of the reactor was lowered to room temperature to stop the reaction.
  • the composition of the product obtained from the reaction was analyzed by liquid chromatography. The conversion rate of cyclohexyl acetate was 100%, the yield of adipic acid was 96.6%, the yield of glutaric acid was 3.1%, and the yield of succinic acid was 0.1%.
  • the product obtained from the addition reaction was distilled to obtain cyclohexyl acetate with a purity greater than 99.5%.
  • the cyclohexyl acetate was further subjected to an oxidation reaction, and the specific steps of the oxidation reaction were as follows: 105.0 g of 60% nitric acid is added to a 250 ml reactor, and 2.2 g of copper nitrate trihydrate and 0.07 g of ammonium metavanadate as catalysts were added therein respectively.
  • the temperature of the reactor was raised to 70° C. Vigorous stirring was performed to dissolve the catalyst. 17.8 g of cyclohexyl acetate obtained from the addition reaction was added to the reaction solution.
  • the reaction was performed under stirring conditions for 40 minutes.
  • the temperature of the reactor was lowered to room temperature to stop the reaction.
  • the composition of the product obtained from the reaction was analyzed by liquid chromatography. The conversion rate of cyclohexyl acetate was 100%, the yield of adipic acid was 96.1%, the yield of glutaric acid was 3.5%, and the yield of succinic acid was 0.1%.
  • the product obtained from the addition reaction was distilled to obtain cyclohexyl acetate with a purity greater than 99.5%.
  • the cyclohexyl acetate was further subjected to an oxidation reaction, and the specific steps of the oxidation reaction were as follows: 78.8 g of 60% nitric acid was added to a 250 ml reactor, and 0.6 g of copper nitrate trihydrate and 0.02 g of ammonium metavanadate as catalysts were added therein respectively. The temperature of the reactor was raised to 70° C. Vigorous stirring was performed to dissolve the catalyst. 17.8 g of cyclohexyl acetate obtained from the addition reaction was added to the reaction solution. The reaction was performed under stirring conditions for 40 minutes.
  • the product obtained from the addition reaction was distilled to obtain cyclohexyl acetate with a purity greater than 99.5%.
  • the cyclohexyl acetate was further subjected to an oxidation reaction, and the specific steps of the oxidation reaction were as follows: 63.1 g of 50% nitric acid was added to a 250 ml reactor, and 1.0 g of copper nitrate trihydrate and 0.04 g of ammonium metavanadate as catalysts were added therein respectively. The temperature of the reactor was raised to 70° C. Vigorous stirring was performed to dissolve the catalyst. 17.8 g of cyclohexyl acetate obtained from the addition reaction was added to the reaction solution. The reaction was performed under stirring conditions for 40 minutes.
  • the product obtained from the addition reaction was distilled to obtain cyclohexyl acetate with a purity greater than 99.5%.
  • the cyclohexyl acetate was further subjected to an oxidation reaction, and the specific steps of the oxidation reaction are as follows: 87.5 g of 45% nitric acid was added to a 250 ml reactor, and 1.7 g of copper nitrate trihydrate and 0.04 g of ammonium metavanadate as catalysts were added therein respectively. The temperature of the reactor was raised to 70° C. Vigorous stirring was performed to dissolve the catalyst. 17.8 g of cyclohexyl acetate obtained from the addition reaction was added to the reaction solution. The reaction was performed under stirring conditions for 60 minutes.
  • DA330 macroporous strong acid ion exchange resin
  • the temperature of the reactor was raised to 90° C., and the reaction pressure was 0.1 MPa.
  • the cyclohexene and acetic acid as reactants were fed into the reactor respectively, wherein the molar ratio of acetic acid to cyclohexene was 4:1.
  • the space velocity of cyclohexene was 1.0 g ⁇ g ⁇ 1 ⁇ h ⁇ 1 .
  • the reaction was continuously run for 250 hours.
  • the product obtained from the addition reaction was distilled to obtain cyclohexyl acetate with a purity greater than 99.5%.
  • the cyclohexyl acetate was further subjected to an oxidation reaction, and the specific steps of the oxidation reaction are as follows: 110.3 g of 50% nitric acid is added to a 250 ml reactor, and 1.7 g of copper nitrate trihydrate and 0.08 g of ammonium metavanadate as catalysts are added therein respectively.
  • the temperature of the reactor was raised to 50° C. Vigorous stirring was performed to dissolve the catalyst. 17.8 g of cyclohexyl acetate obtained from the addition reaction was added to the reaction solution. The reaction was performed under stirring conditions for 60 minutes.
  • the product obtained from the addition reaction was distilled to obtain cyclohexyl acetate with a purity greater than 99.5%.
  • the cyclohexyl acetate was further subjected to an oxidation reaction, and the specific steps of the oxidation reaction were as follows: 110.3 g of 50% nitric acid was added to a 250 ml reactor, and 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate as catalysts were added therein respectively. The temperature of the reactor was raised to 40° C. Vigorous stirring was performed to dissolve the catalyst. 17.8 g of cyclohexyl acetate obtained from the addition reaction was added to the reaction solution. The reaction was performed under stirring conditions for 60 minutes.
  • the product obtained from the addition reaction was distilled to obtain cyclohexyl acetate with a purity greater than 99.5%.
  • the cyclohexyl acetate was further subjected to an oxidation reaction, and the specific steps of the oxidation reaction were as follows: 110.3 g of 50% nitric acid is added to a 250 ml reactor, and 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate as catalysts were added therein respectively. The temperature of the reactor was raised to 60° C. Vigorous stirring was performed to dissolve the catalyst. 17.8 g of cyclohexyl acetate obtained from the addition reaction was added to the reaction solution. The reaction was performed under stirring conditions for 40 minutes.
  • HNV-8 macroporous strong acid ion exchange resin
  • the temperature of the reactor was raised to 90° C., and the reaction pressure was 0.1 MPa.
  • the cyclohexene and acetic acid as reactants were fed into the reactor respectively, wherein the molar ratio of acetic acid to cyclohexene is 4:1.
  • the space velocity of cyclohexene was 1.0 g ⁇ g ⁇ 1 ⁇ h ⁇ 1 .
  • the reaction was continuously run for 250 hours. After the reaction product was collected, the composition thereof was analyzed by gas chromatography.
  • the conversion rate of cyclohexene was 84.6%, and the selectivity of cyclohexyl acetate was 98.3%.
  • the product obtained from the addition reaction was distilled to obtain cyclohexyl acetate with a purity greater than 99.5%.
  • the cyclohexyl acetate was further subjected to an oxidation reaction, and the specific steps of the oxidation reaction were as follows: 110.3 g of 50% nitric acid is added to a 250 ml reactor, and 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate as catalysts were added therein respectively. The temperature of the reactor was raised to 80° C. Vigorous stirring was performed to dissolve the catalyst. 17.8 g of cyclohexyl acetate obtained from the addition reaction was added to the reaction solution. The reaction was performed under stirring conditions for 30 minutes.
  • 60 ml of the supported phosphotungstic acid catalyst HPW/SiO 2 was loaded into the middle of a stainless steel tubular fixed bed reactor, and the upper and lower parts of the middle of the stainless steel tubular fixed bed reactor where the catalyst was located were filled with quartz sand respectively.
  • the temperature of the reactor was raised to 100° C., and the reaction pressure was 2.0 MPa.
  • the cyclohexene and acetic acid as reactants were fed into the reactor respectively, wherein the molar ratio of acetic acid to cyclohexene is 4:1.
  • the space velocity of cyclohexene was 1.0 g ⁇ g ⁇ 1 ⁇ h ⁇ 1 .
  • the reaction was continuously run for 250 hours. After the reaction product was collected, the composition thereof was analyzed by gas chromatography.
  • the conversion rate of cyclohexene was 80.7%, and the selectivity of cyclohexyl acetate was 97.8%.
  • the product obtained from the addition reaction was distilled to obtain cyclohexyl acetate with a purity greater than 99.5%.
  • the cyclohexyl acetate was further subjected to an oxidation reaction, and the specific steps of the oxidation reaction were as follows: 110.3 g of 50% nitric acid was added to a 250 ml reactor, and 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate as catalysts were added therein respectively. The temperature of the reactor was raised to 90° C. Vigorous stirring was performed to dissolve the catalyst. 17.8 g of cyclohexyl acetate obtained from the addition reaction was added to the reaction solution. The reaction was performed under stirring conditions for 30 minutes.
  • the conversion rate of cyclohexene was 81.2%, and the selectivity of cyclohexyl acetate was 97.6%.
  • the product obtained from the addition reaction was distilled to obtain cyclohexyl acetate with a purity greater than 99.5%.
  • the cyclohexyl acetate was further subjected to an oxidation reaction, and the specific steps of the oxidation reaction were as follows: 110.3 g of 50% nitric acid was added to a 250 ml reactor, and 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate as catalysts were added therein respectively. The temperature of the reactor was raised to 100° C. Vigorous stirring was performed to dissolve the catalyst. 17.8 g of cyclohexyl acetate obtained from the addition reaction was added to the reaction solution.
  • the reaction was performed under stirring conditions for 30 minutes. Then the temperature of the reactor was lowered to room temperature to stop the reaction. The composition of the product obtained from the reaction was analyzed by liquid chromatography. The conversion rate of cyclohexyl acetate was 100%, the yield of adipic acid was 92.1%, the yield of glutaric acid was 4.6%, and the yield of succinic acid was 0.7%.
  • the product obtained from the addition reaction was distilled to obtain cyclohexyl acetate with a purity greater than 99.5%.
  • the cyclohexyl acetate was further subjected to an oxidation reaction, and the specific steps of the oxidation reaction are as follows: 110.3 g of 50% nitric acid was added to a 250 ml reactor, and 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate as catalysts were added therein respectively. The temperature of the reactor was raised to 120° C. Vigorous stirring was performed to dissolve the catalyst. 17.8 g of cyclohexyl acetate obtained from the addition reaction was added to the reaction solution.
  • the reaction was performed under stirring conditions for 20 minutes. Then the temperature of the reactor was lowered to room temperature to stop the reaction. The composition of the product obtained from the reaction was analyzed by liquid chromatography. The conversion rate of cyclohexyl acetate was 100%, the yield of adipic acid was 90.8%, the yield of glutaric acid was 4.8%, and the yield of succinic acid was 1.0%.
  • the product obtained from the addition reaction was distilled to obtain cyclohexyl acetate with a purity greater than 99.5%.
  • the cyclohexyl acetate was further subjected to an oxidation reaction, and the specific steps of the oxidation reaction were as follows: 110.3 g of 50% nitric acid was added to a 250 ml reactor, and 3.3 g of cobalt nitrate hexahydrate and 0.1 g of ammonium metavanadate as catalysts were added therein respectively. The temperature of the reactor was raised to 70° C. Vigorous stirring was performed to dissolve the catalyst. 17.8 g of cyclohexyl acetate obtained from the addition reaction was added to the reaction solution. The reaction was performed under stirring conditions for 40 minutes.
  • the product obtained from the addition reaction was distilled to obtain cyclohexyl acetate with a purity greater than 99.5%.
  • the cyclohexyl acetate is further subjected to an oxidation reaction, and the specific steps of the oxidation reaction were as follows: 110.3 g of 50% nitric acid was added to a 250 ml reactor, and 2.9 g of ferric nitrate and 0.1 g of ammonium metavanadate as catalysts were added therein respectively. The temperature of the reactor was raised to 70° C. Vigorous stirring was performed to dissolve the catalyst. 17.8 g of cyclohexyl acetate obtained from the addition reaction was added to the reaction solution. The reaction was performed under stirring conditions for 40 minutes.
  • HY molecular sieve catalyst 60 m was loaded into the middle of a stainless steel tubular fixed bed reactor, and the upper and lower parts of the middle of the stainless steel tubular fixed bed reactor where the catalyst was located were filled with quartz sand respectively.
  • the temperature of the reactor was raised to 80° C., and the reaction pressure was 0.1 MPa.
  • the cyclohexene and acetic acid as reactants were fed into the reactor respectively, wherein the molar ratio of acetic acid to cyclohexene was 4:1.
  • the space velocity of cyclohexene was 1.0 g ⁇ g ⁇ 1 ⁇ h ⁇ 1 .
  • the reaction was continuously run for 250 hours. After the reaction product was collected, the composition thereof was analyzed by gas chromatography.
  • the conversion rate of cyclohexene was 62.3%, and the selectivity of cyclohexyl acetate was 98.4%.
  • the product obtained from the addition reaction was distilled to obtain cyclohexyl acetate with a purity greater than 99.5%.
  • the cyclohexyl acetate was further subjected to an oxidation reaction, and the specific steps of the oxidation reaction were as follows: 99.2 g of 20% hydrogen peroxide was added to a 250 ml reactor, and 2.3 g of phosphomolybdic acid was added therein. The temperature of the reactor was raised to 80° C. Vigorous stirring was performed to dissolve the catalyst. 17.8 g of cyclohexyl acetate obtained from the addition reaction was added to the reaction solution. The reaction was performed under stirring conditions for 60 minutes. Then the temperature of the reactor was lowered to room temperature to stop the reaction.
  • the composition of the product obtained from the reaction was analyzed by liquid chromatography.
  • the conversion rate of cyclohexyl acetate was 100%, the yield of adipic acid was 85.6%, the yield of glutaric acid was 9.8%, and the yield of succinic acid was 2.3%.
  • HZSM-5 molecular sieve catalyst 60 m of HZSM-5 molecular sieve catalyst was loaded into the middle of a stainless steel tubular fixed-bed reactor, and the upper and lower parts of the middle of the stainless steel tubular fixed bed reactor where the catalyst was located were filled with quartz sand respectively.
  • the temperature of the reactor was raised to 80° C., and the reaction pressure was 0.1 MPa.
  • the cyclohexene and acetic acid as reactants were fed into the reactor respectively, wherein the molar ratio of acetic acid to cyclohexene was 4:1.
  • the space velocity of cyclohexene was 1.0 g ⁇ g ⁇ 1 ⁇ h ⁇ 1 .
  • the reaction was continuously run for 250 hours. After the reaction product was collected, the composition thereof was analyzed by gas chromatography.
  • the conversion rate of cyclohexene was 71.4%, and the selectivity of cyclohexyl acetate was 98.9%.
  • the product obtained from the addition reaction was distilled to obtain cyclohexyl acetate with a purity greater than 99.5%.
  • the cyclohexyl acetate was further subjected to an oxidation reaction, and the specific steps of the oxidation reaction were as follows: 99.2 g of 20% hydrogen peroxide was added to a 250 ml reactor, and 3.8 g of ammonium tungstate was added therein. The temperature of the reactor was raised to 80° C. Vigorous stirring was performed to dissolve the catalyst. 17.8 g of cyclohexyl acetate obtained from the addition reaction was added to the reaction solution. The reaction was performed under stirring conditions for 60 minutes. Then the temperature of the reactor was lowered to room temperature to stop the reaction.
  • the composition of the product obtained from the reaction was analyzed by liquid chromatography.
  • the conversion rate of cyclohexyl acetate was 100%
  • the yield of adipic acid was 82.1%
  • the yield of glutaric acid was 10.4%
  • the yield of succinic acid was 3.6%.
  • the unreacted cyclohexene was separated from the product obtained from the addition reaction to obtain a mixture mainly comprising acetic acid and cyclohexyl acetate, wherein the molar ratio of acetic acid to cyclohexyl acetate was 3.7.
  • the mixture of acetic acid/cyclohexyl acetate was further subjected to an oxidation reaction, and the specific steps of the oxidation reaction were as follows: 110.3 g of 50% nitric acid was added to a 250 ml reactor, and 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate were added therein respectively. The temperature of the reactor was raised to 70° C. Vigorous stirring was performed to dissolve the catalyst.
  • the unreacted cyclohexene was separated from the product obtained from the addition reaction to obtain a mixture mainly comprising acetic acid and cyclohexyl acetate, wherein the molar ratio of acetic acid to cyclohexyl acetate was 6.4.
  • the mixture of acetic acid/cyclohexyl acetate was further subjected to an oxidation reaction, and the specific steps of the oxidation reaction were as follows: 110.3 g of 50% nitric acid was added to a 250 ml reactor, and 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate were added therein respectively. The temperature of the reactor was raised to 70° C. Vigorous stirring was performed to dissolve the catalyst.
  • the product obtained from the addition reaction was distilled to obtain cyclohexyl acetate with a purity greater than 99.5%.
  • the cyclohexyl acetate was further subjected to an oxidation reaction.
  • the specific steps of the reaction were as follows: 110.3 g of 50% nitric acid was added into a 250 ml reactor, and 1.1 g (NH 4 ) 6 Mo 7 O 24 and 0.1 g ammonium metavanadate were added therein respectively.
  • the temperature of the reactor was raised to 70° C. Vigorous stirring was performed to dissolve the catalyst. 17.8 g of cyclohexyl acetate obtained from the addition reaction was added to the reaction solution.
  • the reaction was performed under stirring conditions for 40 minutes.
  • the product obtained from the addition reaction was distilled to obtain cyclohexyl acetate with a purity greater than 99.5%.
  • the cyclohexyl acetate was further subjected to an oxidation reaction.
  • the specific steps of the reaction were as follows: 110.3 g of 50% nitric acid was added into a 250 ml reactor, and 1.4 g (NH 4 ) 2 MoO 4 and 0.1 g ammonium metavanadate were added therein respectively.
  • the temperature of the reactor was raised to 70° C. Vigorous stirring was performed to dissolve the catalyst. 17.8 g of cyclohexyl acetate obtained from the addition reaction was added to the reaction solution.
  • the reaction was performed under stirring conditions for 40 minutes.
  • DA330 macroporous strong acid ion exchange resin
  • the temperature of the reactor was increased to 100° C., and the reaction pressure was 2.0 MPa.
  • the cyclohexene and acetic acid as reactants were fed into the reactor respectively, wherein the molar ratio of acetic acid to cyclohexene was 2:1.
  • the space velocity of cyclohexene was 2.0 g ⁇ g ⁇ 1 ⁇ h ⁇ 1 .
  • the reaction was continuously run for 250 hours. After the reaction product was collected, the composition thereof was analyzed by gas chromatography.
  • the conversion rate of cyclohexene was 76.5%, and the selectivity of cyclohexyl acetate was 98.6%.
  • the unreacted cyclohexene was separated from the product obtained from the addition reaction to obtain a mixture mainly comprising acetic acid and cyclohexyl acetate, wherein the molar ratio of acetic acid to cyclohexyl acetate was 1.6.
  • the mixture of acetic acid/cyclohexyl acetate was further subjected to an oxidation reaction, and the specific steps of the oxidation reaction were as follows: 110.3 g of 50% nitric acid was added to a 250 ml reactor, and 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate were added therein respectively. The temperature of the reactor was raised to 70° C. Vigorous stirring was performed to dissolve the catalyst.
  • the product obtained from the addition reaction was distilled to obtain cyclohexyl acetate with a purity greater than 99.5%.
  • the cyclohexyl acetate was further subjected to an oxidation reaction, and the specific steps of the oxidation reaction were as follows: 110.3 g of 50% nitric acid was added to a 250 ml reactor, and 2.5 g of copper nitrate trihydrate was added therein. The temperature of the reactor was raised to 70° C. Vigorous stirring was performed to dissolve the catalyst. 17.8 g of cyclohexyl acetate obtained from the addition reaction was added to the reaction solution. The reaction was performed under stirring conditions for 40 minutes. Then the temperature of the reactor was lowered to room temperature to stop the reaction.
  • the composition of the product obtained from the reaction was analyzed by liquid chromatography.
  • the conversion rate of cyclohexyl acetate was 100%
  • the yield of adipic acid was 83.3%
  • the yield of glutaric acid was 12.4%
  • the yield of succinic acid was 2.5%.
  • the product obtained from the addition reaction was distilled to obtain cyclohexyl acetate with a purity greater than 99.5%.
  • the cyclohexyl acetate was further subjected to an oxidation reaction, and the specific steps of the oxidation reaction were as follows: 110.3 g of 50% nitric acid was added to a 250 ml reactor, and 0.1 g of ammonium metavanadate was added therein. The temperature of the reactor was raised to 70° C. Vigorous stirring was performed to dissolve the catalyst. 17.8 g of cyclohexyl acetate obtained from the addition reaction was added to the reaction solution. The reaction was performed under stirring conditions for 40 minutes. Then the temperature of the reactor was lowered to room temperature to stop the reaction.
  • the composition of the product obtained from the reaction was analyzed by liquid chromatography.
  • the conversion rate of cyclohexyl acetate was 100%
  • the yield of adipic acid was 81.2%
  • the yield of glutaric acid was 13.5%
  • the yield of succinic acid was 2.6%.
  • the product obtained from the addition reaction was distilled to obtain cyclohexyl acetate with a purity greater than 99.5%.
  • the cyclohexyl acetate was further subjected to an oxidation reaction, and the specific steps of the oxidation reaction were as follows: 110.3 g of 50% nitric acid was added to a 250 ml reactor, and 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate were added therein respectively. The temperature of the reactor was raised to 70° C. Vigorous stirring was performed to dissolve the catalyst. 17.8 g of cyclohexyl acetate obtained from the addition reaction was added to the reaction solution. The reaction was performed under stirring conditions for 40 minutes.
  • the temperature of the reactor was lowered to room temperature to stop the reaction.
  • the composition of the product obtained from the reaction was analyzed by liquid chromatography. The conversion rate of cyclohexyl acetate was 100%, the yield of adipic acid was 96.7%, the yield of glutaric acid was 2.7%, and the yield of succinic acid was 0.1%.
  • the product obtained from the addition reaction was distilled to obtain cyclopentyl acetate with a purity greater than 99.5%.
  • the cyclopentyl acetate was further subjected to an oxidation reaction, and the specific steps of the oxidation reaction were as follows: 110.3 g of 50% nitric acid was added to a 250 ml reactor, and 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate were added therein respectively. The temperature of the reactor was raised to 70° C. Vigorous stirring was performed to dissolve the catalyst. 16.0 g of cyclopentyl acetate obtained from the addition reaction was added to the reaction solution. The reaction was performed under stirring conditions for 40 minutes.
  • the product obtained from the addition reaction was distilled to obtain cyclohexyl acetate with a purity greater than 99.5%.
  • the cyclohexyl acetate was further subjected to an oxidation reaction, and the specific steps of the oxidation reaction were as follows: 78.8 g of 50% nitric acid was added to a 250 ml reactor, and 0.96 g of copper nitrate trihydrate and 0.07 g of ammonium metavanadate were added therein respectively. The temperature of the reactor was raised to 70° C. Vigorous stirring was performed to dissolve the catalyst. 17.8 g of cyclohexyl acetate obtained from the addition reaction was added to the reaction solution. The reaction was performed under stirring conditions for 40 minutes.
  • the product obtained from the addition reaction was distilled to obtain cycloheptyl formate with a purity greater than 99.5%.
  • the cycloheptyl formate was further subjected to an oxidation reaction, and the specific steps of the oxidation reaction were as follows: 110.3 g of 50% nitric acid was added to a 250 ml reactor, and 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate were added therein respectively. The temperature of the reactor was raised to 70° C. Vigorous stirring was performed to dissolve the catalyst. 17.8 g of cycloheptyl formate obtained from the addition reaction was added to the reaction solution. The reaction was performed under stirring conditions for 40 minutes.
  • the composition of the product obtained from the reaction was analyzed by liquid chromatography.
  • the conversion rate of cycloheptyl formate was 100%, the yield of pimelic acid was 95.6%, the yield of adipic acid was 3.4%, and the yield of glutaric acid was 0.5%.
  • the product obtained from the addition reaction was distilled to obtain cyclohexyl acrylate with a purity greater than 99.5%.
  • the cyclohexyl acrylate was further subjected to an oxidation reaction, and the specific steps of the oxidation reaction were as follows: 110.3 g of 50% nitric acid was added to a 250 ml reactor, and 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate were added therein respectively. The temperature of the reactor was raised to 70° C. Vigorous stirring was performed to dissolve the catalyst. 19.3 g of cyclohexyl acrylate obtained from the addition reaction was added to the reaction solution. The reaction was performed under stirring conditions for 40 minutes.
  • the temperature of the reactor was lowered to room temperature to stop the reaction.
  • the composition of the product obtained from the reaction was analyzed by liquid chromatography.
  • the conversion rate of cyclohexyl acrylate was 100%, the yield of adipic acid was 95.1%, the yield of glutaric acid was 3.5%, and the yield of succinic acid was 0.6%.
  • the product obtained from the addition reaction was distilled to obtain cyclohexyl trifluoroacetate with a purity greater than 99.5%.
  • the cyclohexyl trifluoroacetate was further subjected to an oxidation reaction, and the specific steps of the oxidation reaction were as follows: 110.3 g of 50% nitric acid was added to a 250 ml reactor, and 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate were added therein respectively. The temperature of the reactor was raised to 70° C. Vigorous stirring was performed to dissolve the catalyst. 24.5 g of cyclohexyl trifluoroacetate obtained from the addition reaction was added to the reaction solution. The reaction was performed under stirring conditions for 40 minutes.
  • the product obtained from the addition reaction was distilled to obtain chlorocyclohexyl acetate with a purity greater than 99.5%.
  • the chlorocyclohexyl acetate was further subjected to an oxidation reaction, and the specific steps of the oxidation reaction were as follows: 110.3 g of 50% nitric acid was added to a 250 ml reactor, and 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate were added therein respectively. The temperature of the reactor was raised to 70° C. Vigorous stirring was performed to dissolve the catalyst. 22.1 g of chlorocyclohexyl acetate obtained from the addition reaction was added to the reaction solution. The reaction was performed under stirring conditions for 40 minutes.
  • the product obtained from the addition reaction was distilled to obtain methylcyclohexyl acetate with a purity greater than 99.5%.
  • the methylcyclohexyl acetate was further subjected to an oxidation reaction, and the specific steps of the oxidation reaction were as follows: 110.3 g of 50% nitric acid was added to a 250 ml reactor, and 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate were added therein respectively. The temperature of the reactor was raised to 70° C. Vigorous stirring was performed to dissolve the catalyst. 19.5 g of methylcyclohexyl acetate obtained from the addition reaction was added to the reaction solution. The reaction was performed under stirring conditions for 40 minutes.
  • the product obtained from the addition reaction was distilled to obtain cyclohexyl acetate with a purity greater than 99.5%.
  • the cyclohexyl acetate was further subjected to an oxidation reaction, and the specific steps of the oxidation reaction were as follows: 78.8 g of 50% nitric acid was added to a 250 ml reactor, and 0.48 g of copper nitrate trihydrate and 0.07 g of ammonium metavanadate were added therein respectively. The temperature of the reactor was raised to 60° C. Vigorous stirring was performed to dissolve the catalyst. 17.8 g of cyclohexyl acetate obtained from the addition reaction was added to the reaction solution. The reaction was performed under stirring conditions for 60 minutes.
  • the product obtained from the addition reaction was distilled to obtain cyclohexyl acetate with a purity greater than 99.5%.
  • the cyclohexyl acetate was further subjected to an oxidation reaction, and the specific steps of the oxidation reaction were as follows: 110.3 g of 50% nitric acid was added to a 250 ml reactor, and 2.5 g of copper nitrate trihydrate and 0.1 g of ammonium metavanadate were added therein respectively. The temperature of the reactor was raised to 70° C. Vigorous stirring was performed to dissolve the catalyst. 17.8 g of cyclohexyl acetate obtained from the addition reaction was added to the reaction solution. The reaction was performed under stirring conditions for 40 minutes.
  • the temperature of the reactor was lowered to room temperature to stop the reaction.
  • the composition of the product obtained from the reaction was analyzed by liquid chromatography. The conversion rate of cyclohexyl acetate was 100%, the yield of adipic acid was 96.8%, the yield of glutaric acid was 2.6%, and the yield of succinic acid was 0.1%.

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